JPH0440702B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a color photographic material containing a novel coupler. For the formation of color photographic images based on the subtractive color method, an aromatic primary amine compound, particularly an N,N-disubstituted paraphenylene diamine compound, is used as a developing agent to halogenate a photographic emulsion that has been exposed or chemically fogged. A process is utilized to provide cyan, magenta and yellow dye images by reducing the silver particles and reacting the coupler with the acid product of the developing agent formed at the same time. The coupler for the above color development method is a compound having a phenolic hydroxyl group, an aniline amino group, an active methylene group or an active methine group, and provides a dye by oxidative coupling with an aromatic primary amine developing agent. . Couplers that react with oxidized color developing agents to form cyan dyes include phenols and naphthols. Couplers that form magenta dyes include pyrazolone, pyrazolotriazole, pyrazolobenzimidazole, indazolone, cyanoacetophenone, and thiaminoaniline. Couplers that form yellow dyes include alphaacylacetamide, beta-ketoacetoacetate, beta-diketone, and N,N-malondiamide. Various methods have been devised for adding couplers such as those mentioned above to photographic emulsion layers.
Introducing a lipophilic ballast group into the coupler molecule,
A method in which the compound is added by dissolving it in an organic solvent and emulsifying it is useful. The following properties are necessary for a coupler having a lipophilic ballast group in order to produce a color light-sensitive material with excellent photographic performance. That is, (1) the coupler and the coloring dye produced during color development have high solubility in the high-boiling organic solvent used for dispersing the coupler (for example, trigreyl phosphate); (2) High stability after dispersion in a silver halide photographic emulsion, and a stable coating film without precipitation of coupler crystals even after coating and drying on a support. (3) It has excellent diffusion resistance and does not diffuse to other layers. (4) Good dyeability, excellent spectral absorption characteristics of the dyed dye image, and high color, density, and fastness to light of the dye image. (5) Cheap and simple synthesis method from raw materials with good reproducibility;
and can be obtained in high yield. etc. Conventionally, many attempts have been made to modify the structure of the ballast group in order to improve these properties. As an example of these attempts,
No., Special Publication No. 46-5391, Special Publication No. 39-27563, U.S. Patent No. 2589004, U.S. Patent No. 2908573, U.S. Pat.
No., US Patent No. 2474293, US Patent No. 2039970, US Patent No. 2920961, Special Publication No. 1974-36078, US Patent No.
No. 2589004, Brit No. 944838, Special Publication No. 1977-19026,
U.S. Patent No. 2659329, Brit No. 1813832, JP-A-53-
No. 76834, JP 54-36856, JP 53-82411
No., OLS2707488, JP 53-139534, JP 53-141622, JP 54-23528, JP 54
−48541, JP-A No. 1983-65035, JP-A-1983-
No. 99433, JP-A-54-121126, etc. can be mentioned. However, conventionally known couplers having a ballast group have some defects and do not fully satisfy the above-mentioned necessary properties. these,
Couplers with lipophilic ballast groups are superior to couplers of other series (for example, those with acid groups) in terms of stability in the emulsion layer, diffusion resistance, spectral absorption characteristics of color images, stability of color images, and suitability for synthesis. Although many of them are superior to couplers (which are added to the emulsion layer as a micellar aqueous solution), no one has yet been found that is satisfactory in terms of color development. In high-temperature rapid processing, which has recently become popular, color development is particularly important, and insufficient color development becomes a serious problem. In order to compensate for this insufficient color development, in some cases, an organic solvent such as benzyl alcohol is added to the developer as a color development promoter. However, these organic solvents for promoting color development have several drawbacks. For example, during the development process, it is absorbed into the emulsion layer, so the amount in the developer decreases, resulting in a decrease in color development. It is carried into bleach or bleach-fix solutions, inhibiting desilvering and reducing dye density. It remains in the photosensitive material after processing and reduces color image stability. B, O, D,
It causes an increase in C・O・D. It is highly desirable to remove or reduce the amount of organic solvents used to promote color development. The first object of the present invention is to provide a coupler suitable for producing a color photographic material having excellent photographic properties, particularly color development. A second object of the present invention is to provide a color photographic material having a silver halide emulsion containing a coupler having a novel substituent. The third object of the present invention is to use a coupler having a novel substituent to produce color photographs that have sufficient color development even when organic solvents for promoting color development such as benzyl alcohol are removed or reduced from the color developer. Our purpose is to provide photosensitive materials. A fourth object of the present invention is to provide a color photographic material suitable for rapid processing at high temperatures by using a new coupler. These objects of the present invention have been achieved by a color photographic light-sensitive material containing a coupler characterized by having a diffusion-resistant group represented by the following general formula () at a bonding position other than the coupling position. General formula () -O-(CH ₂ ) _w ---S(O) _v ---R In the formula, w represents an integer from 2 to 6, v represents an integer from 0 to 2, and R is the number of carbon atoms. represents a substituted or unsubstituted chain, cyclic or branched, saturated or unsaturated alkyl group, or a substituted or unsubstituted aryl group of 6 or more. Here, the definition of coupler includes the known compounds described below. Cyan coupler residues include phenol and naphthol; magenta coupler residues include pyrazolone, pyrazolotriazole, pyrazolobenziminazole, indazolone, cyanoacetophenone, and 4-aminoaniline; and yellow coupler residues include alpha. Examples include acylacetamide, beta-ketoacetate, beta-diketone, and N,N-malondiamide. In addition to these, resorcinol, 3-aminophenol, and the like can be mentioned as coupler residues that form black or gray dyes by reaction with oxidized color developing agents. In addition, examples of the coupler residue that reacts with the oxidized color developing agent to form a colorless compound include indanone, acetophenone, and the like. The coupler residue may have a substituent other than a hydrogen atom at a position (coupling position) that causes a coupling reaction with the oxidized color developing agent. Among the couplers of the present invention, those useful are represented by the following general formula () or (). General formula () X-A-O(-CH ₂ ) _w ---S(O) _v ---R General formula () A-X-O(-CH ₂ ) _w ---S(O) _v ---R In the formula, R, w and v represent the same meanings as defined in the general formula (), A represents a coupling group, and X represents an organic residue bonded to the coupling position of the coupling group A. . The total number of carbon atoms contained in R is preferably 6 or more and 40 or less. In the formula, when R represents a substituted alkyl group, preferred substituents are those listed below. Aryl group, alkoxycarbonyl group, hydroxyl group,
These are an acylamino group, an alkanoyl group, an aryloxy group, a carboxyl group, a halogen atom, a carbamoyl group, an acyloxy group, or an imide group. In the formula, when R represents an aryl group, a phenyl group is preferred and the substituents are selected from those listed below. chain, cyclic or branched alkyl group,
Alkoxy group, alkoxycarbonyl group, acylamino group, aryl group, carbamoyl group, acyloxy group, halogen atom, hydroxy group, carboxyl group, carbamoyl group, N-alkyl (or N-aryl)carbamoyl group, sulfamoyl group, N-alkyl group ( or N-aryl)
Sulfamoyl group, imide group, ureido group, N-
an alkyl (or N-aryl) ureido group,
An aryloxy group, an alkyl (or aryl)sulfonyl group, an alkyl or arylsulfonamido group, a cyano group, an amino group, or an alkylthio group. In the formula, when A represents a yellow image-forming coupling group, it specifically refers to pivaloylacetanilide type, benzoylacetanilide type, malondiester type, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, malone ester monoamide type. , benzothiazolylacetate type, benzoxazolyl acetamide type, benzoxazolyl acetate type, benzimidazolylacetamide type or benzimidazolylacetate type coupler residue, heterocycle-substituted acetamide or heterocycle included in U.S. Pat. No. 3,841,880 Coupler residue derived from substituted acetate or US Patent No. 3770446, British Patent No. 1459171, West German Patent (OLS) No. 2503099, Japanese Patent Publication No. 50-
No. 139738 or Research Disclosure
Examples include coupler residues derived from acylacetamides described in No. 15737 and heterocyclic coupler residues described in US Pat. No. 4,046,574. When A represents a magenta color image forming coupling group, specifically 5-oxo-2-pyrazoline type,
Examples include pyrazolone benzimidazole type, pyrazolotriazole type, cyanoacetophenone type, and N-heterocycle-substituted acylacetamide type coupler residues described in OLS No. 3121955. When A represents a cyan image-forming coupling group, mention may be made of coupler residues having a phenol nucleus or an alpha-naphthol nucleus. When A represents a coupling group that does not substantially form a dye, examples of this type of coupler residue include indanone type and acetophenone type coupler residues, and specifically, US Pat. No. 4,052,213;
Same No. 4088491, No. 3632345, No. 3958993, Same No.
It is described in No. 3961959, No. 4046574, or No. 3938996. As X bonded to the coupling position of the coupler, a known coupling-off group can be used in the general formula (). In the general formula (), X may be a known leaving group or a hydrogen atom. The leaving group used in the general formula () is an atomic group bonded to the coupling position of the coupler component A with a nitrogen atom, oxygen atom, carbon atom, or sulfur atom, and in addition, in the general formula (), it is a halogen atom. is described below. Alkoxy group, acyloxy group, aryloxy group, arylthio group, heterocyclic thio group, alkylthio group, sulfonamide group, heterocyclic oxy group, nitrogen-containing 5- or 6-membered heterocyclic group (at least one nitrogen atom It contains an atom and bonds to the active position of the coupler moiety through a nitrogen atom.For example, imidazolyl group, triazolyl group, 2,
4-dioxoimidazolidinyl group, 3,5-dioxo-1,2,4-triazolidinyl group, pyrazolyl group, etc.), benzene-fused ring heterocyclic group (e.g. benzotriazolyl group, benzimidazolyl group, etc.), arylazo group , chlorine atom, aliphatic aminomethyl group, etc. When these leaving groups are X in the general formula (), they may have the following substituents at substitutable positions, and through those which can be divalent groups among the following substituents: , or directly has a group of general formula (). Furthermore, when the aforementioned leaving group is X in the general formula (), they may have the following substituents at substitutable positions. Number of carbon atoms: 1 to 32, preferably 1
~10 saturated or unsaturated cyclic, linear or branched alkyl groups, aryl groups having 6 to 10 carbon atoms, halogen atoms, cyano groups, nitro groups, nitroso groups,
Carboxy group, carbamoyl group, sulfo group, hydroxy group, amino group, sulfamoyl group, ureido group, alkoxy group having 1 to 32 carbon atoms, preferably 1 to 10 (the same applies below), acylamino group, alkoxycarbonyl group, alkoxycarbonylamino group, alkylsulfonamide group, N-alkyl (or N,N-dialkyl)sulfamoyl group,
N-alkyl (or N,N-dialkyl) carbamoyl group, alkanesulfonyl group, alkanoyl group, alkanoyloxy group, alkylthio group,
Aryloxy group having 6 to 10 carbon atoms (the same applies below),
Examples include aryloxycarbonyl group, arylsulfonamide group, N-arylsulfamoyl group, arylsulfonyl group, arylthio group, arylcarbonyl group, N-arylcarbamoyl group, arylureido group, and aryloxycarbamoyl group. Furthermore, the present invention is particularly effective because in the general formulas () and (), A is the following general formula (),
(), (), (), (), (), (), (
),
When it is a coupler residue represented by (), () or (). These couplers are preferred because of their high coupling speed. General formula () General formula () General formula () General formula () General formula () General formula () General formula () General formula () General formula () General formula () General formula () In the above formula, the free bond derived from the coupling position represents the bonding position of the coupling-off group. In the above formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ ,
When R ₇ , R ₈ , R ₉ , R ₁₀ or R ₁₁ contains a diffusion-resistant group, the total number of carbon atoms is 8 to 32, preferably 10 to 22
otherwise the total number of carbons is 15 or less, preferably 10 or less. In the formula, R ₁ represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and R ₂ and R ₃ each represent an aromatic group or a heterocyclic group. In the formula, the aliphatic group represented by R ₁ preferably has 1 to 22 carbon atoms and may be substituted or unsubstituted, chain or cyclic. Preferred substituents for the alkyl group include an alkoxy group, an aryloxy group, an amino group, an acylamino group, and a halogen atom, which may themselves have further substituents. Specific examples of aliphatic groups useful as R ₁ are:
Such as: isopropyl, isobutyl, tert-butyl, isoamyl, tert-
amyl group, 1,1-dimethylbutyl group, 1,1-
Dimethylhexyl group, 1,1-diethylhexyl group, dodecyl group, hexadecyl group, octadecyl group, cyclohexyl group, 2-methoxyisopropyl group, 2-phenoxyisopropyl group, 2-p-
tert-butylphenoxyisopropyl group, α-aminoisopropyl group, α-(diethylamino)isopropyl group, α-(succinimide)isopropyl group, α-(phthalimido)isopropyl group,
α-(benzenesulfonamido)isopropyl group, etc. R ₁ , R ₂ or R ₃ is an aromatic group (especially phenyl group)
In this case, the aromatic group may be substituted. Aromatic groups such as phenyl groups include alkyl groups having 32 or less carbon atoms, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, aliphatic amide groups, alkylsulfamoyl groups, alkylsulfonamide groups, and alkylureido groups. , an alkyl-substituted succinimide group, etc., and in this case, the alkyl group may have an aromatic group such as phenylene interposed in the chain. The phenyl group may also be substituted with an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, etc., and the aryl group of these substituents The moiety may be further substituted with one or more alkyl groups having a total of 1 to 22 carbon atoms. The phenyl group represented by R ₁ , R ₂ or R ₃ further includes an amino group, including one substituted with a lower alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, a sulfo group, a nitro group, a cyano group, It may be substituted with a thiocyano group or a halogen atom. Furthermore, R ₁ , R ₂ or R ₃ may represent a substituent in which a phenyl group is fused with another ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a coumaranyl group, a tetrahydronaphthyl group, and the like. These substituents may themselves have further substituents. When R ₁ represents an alkoxy group, the alkyl portion has 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms.
represents a straight-chain or branched-chain alkyl group, alkenyl group, cyclic alkyl group, or cyclic alkenyl group, which may be substituted with a halogen atom, an aryl group, an alkoxy group, or the like. When R ₁ , R ₂ or R ₃ represents a heterocyclic group,
Each heterocyclic group is bonded to the carbon atom of the carbonyl group of the acyl group or the nitrogen atom of the amide group in the alpha acylacetamide through one of the carbon atoms forming the ring. Such heterocycles include thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyrididine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine,
An example is oxazine. These may further have a substituent on the ring. In the formula, R ₅ has 1 to 32 carbon atoms, preferably 1
to 22 straight-chain or branched alkyl groups (e.g. methyl, isopropyl, tert-butyl, hexyl, dodecyl, etc.), alkenyl groups (e.g. allyl), cyclic alkyl groups (e.g. cyclopentyl, cyclohexyl, norbornyl) ), aralkyl groups (e.g., benzyl, β-phenylethyl, etc.), cyclic alkenyl groups (e.g., cyclopentenyl, cyclohexenyl, etc.), and these include halogen atoms, nitro groups, cyano groups, aryl groups, alkoxy groups, aryl Oxy group, carboxy group, alkylthiocarbonyl group, arylthiocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, thiourethane group, Sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-arylanilino group, N-alkylanilino group, N-acylanilino group group, hydroxy group,
It may be substituted with a mercapto group or the like. Furthermore, R ₅ is an aryl group (e.g. phenyl group,
(α- or β-naphthyl group, etc.) may also be represented. The aryl group may have one or more substituents, such as an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group, and an alkoxy group. group, aryloxy group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-alkylanilino group,
It may have an N-arylanilino group, an N-acylanilino group, a hydroxy group, a mercapto group, etc. More preferred as R ₅ is phenyl in which at least one ortho position is substituted with an alkyl group, an alkoxy group, a halogen atom, etc.
This is useful because the coupler remaining in the film is less likely to change color due to light or heat. Furthermore, R ₅ is a heterocyclic group (for example, a 5- or 6-membered heterocyclic ring containing a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom, a fused heterocyclic group, such as a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group) , oxazolyl group, imidazolyl group, naphthoxazolyl group, etc.), a heterocyclic group substituted with the substituents listed for the above aryl group, an aliphatic or aromatic acyl group, an alkylsulfonyl group, an arylsulfonyl group, It may also represent an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group. In the formula, R ₄ is a hydrogen atom, a straight or branched alkyl having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms,
alkenyl, cyclic alkyl, aralkyl, cyclic alkenyl groups (which may have the substituents listed above for R ₅ ), aryl groups and heterocyclic groups (which may have the substituents listed above for R ₅ ); ), alkoxycarbonyl groups (e.g. methoxycarbonyl group, ethoxycarbonyl group, stearyloxycarbonyl group, etc.),
Aryloxycarbonyl group (e.g. phenoxycarbonyl group, naphthoxycarbonyl group, etc.),
Aralkyloxycarbonyl groups (e.g., benzyloxycarbonyl group, etc.), alkoxy groups (e.g., methoxy, ethoxy, heptadecyloxy, etc.), aryloxy groups (e.g., phenoxy, tolyloxy, etc.), alkylthio groups (e.g., ethylthio, dodecylthio group, etc.), arylthio group (e.g., phenylthio group, α-naphthylthio group, etc.), carboxy group, acylamino group (e.g., acetylamino group, 3-[(2,4-di-
tert-amylphenoxy)astamide]benzamide group, etc.), diacylamino group, N-alkylacylamino group (e.g., N-methylpropionamide group, etc.), N-arylacylamino group (e.g., N-phenylacetamide group, etc.) , ureido groups (e.g. ureido, N-arylureido, N
-alkylureido group), urethane group, thiourethane group, arylamino group (e.g. phenylamino, N-methylanilino group, diphenylamino group, N-acetylanilino group, 2-chloro-5
-tetradecanamide anilino group, etc.), alkylamino groups (e.g. n-butylamino group, methylamino group, cyclohexylamino group, etc.), cycloamino groups (e.g. piperidino group, pyrrolidino group, etc.), heterocyclic amino groups (e.g. -pyridylamino group, 2-benzoxazolylamino group, etc.),
Alkylcarbonyl group (e.g. methylcarbonyl group, etc.), arylcarbonyl group (e.g. phenylcarbonyl group, etc.), sulfonamide group (e.g. alkylsulfonamide group, arylsulfonamide group, etc.), carbamoyl group (e.g. ethylcarbamoyl group, dimethylcarbamoyl group, etc.) group, N-
methyl-phenylcarbamoyl, N-phenylcarbamoyl, etc.), sulfamoyl group (e.g. N-phenylcarbamoyl), sulfamoyl group (e.g.
-alkylsulfamoyl, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N,N-diarylsulfamoyl group, etc.),
Represents any one of a cyano group, a hydroxy group, a mercapto group, a halogen atom, and a sulfo group. In the formula, R ₆ is a hydrogen atom or a carbon number of 1 to 32,
It preferably represents 1 to 22 straight-chain or branched-chain alkyl groups, alkenyl groups, cyclic alkyl groups, aralkyl groups, or cyclic alkenyl groups, which may have the substituents listed for R ₅ above. Furthermore, R ₆ may represent an aryl group or a heterocyclic group, and these may have the substituents listed for R ₅ above. R ₆ is a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, an ureido group, urethane group, sulfonamide group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-arylanilino group, N-alkylanilino group, N- It may also represent an acylanilino group, a hydroxy group or a mercapto group. R ₇ , R ₈ and R ₉ each represent a group used in a typical 4-equivalent phenol or α-naphthol coupler; specifically, R ₇ is a hydrogen atom, a halogen atom, an alkoxycarbonylamino group, an aliphatic carbonized Hydrogen residue, N-arylureido group, acylamino group, -O-R ₁₂ or -S
-R ₁₂ (wherein R ₁₂ is an aliphatic hydrocarbon residue), and when two or more R ₇ exist in the same molecule, the two or more R ₇ may be different groups. Group hydrocarbon residues include those having substituents. In addition, when these substituents contain an aryl group,
The aryl group may have the substituents listed for R ₅ above. Examples of R ₈ and R ₉ include groups selected from aliphatic hydrocarbon residues, aryl groups and heterocyclic residues, or one of these may be a hydrogen atom; Including those with substituents. Further, R ₈ and R ₉ may jointly form a nitrogen-containing heterocyclic nucleus. l is an integer of 1 to 4, m is an integer of 1 to 3, and n is an integer of 1 to 5. The aliphatic hydrocarbon residue may be either saturated or unsaturated, and may be linear, branched, or cyclic.
Preferred are alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl, etc.) and alkenyl groups (e.g., allyl, octenyl, etc.). . Typical aryl groups include phenyl and naphthyl groups, and representative heterocyclic residues include pyridinyl, quinolyl, thienyl, piperidyl, imidazolyl, and the like. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups and heterocyclic residues include halogen atoms, nitro, hydroxy, carboxyl, amino, substituted amino,
Examples include groups such as sulfo, alkyl, alkenyl, aryl, heterocycle, alkoxy, aryloxy, arylthio, arylazo, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, and morpholino. R ₁₀ is an arylcarbonyl group, carbon number 2-32,
Preferably 2-22 alkanoyl group, arylcarbamoyl group, carbon number 2-32, preferably 2-22
represents an alkanecarbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, which may have a substituent, such as an alkoxy group, an alkoxycarbonyl group, acylamino group,
Examples include an alkylsulfamoyl group, an alkylsulfonamide group, an alkylsacinimide group, a halogen atom, a nitro group, a carboxyl group, a nitrile group, an alkyl group, and an aryl group. R ₁₁ is an arylcarbonyl group, carbon number 2-32,
Preferably 2-22 alkanoyl group, arylcarbamoyl group, carbon number 2-32, preferably 2-22
Alkanecarbamoyl group, alkoxycarbonyl group or aryloxycarbonyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, alkanesulfonyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, arylsulfonyl group, aryl group, 5-membered or a 6-membered heterocyclic group (the hetero atom is selected from a nitrogen atom, an oxygen atom, and a sulfur atom, such as a triazolyl group, an imidazolyl group, a phthalimide group, a succinimide group, a furyl group, a pyridyl group, or a benzotriazolyl group) and these are the above
It may have the substituents mentioned in _R10 . As the atomic group represented by X in the general formulas () and (), the following are particularly preferred in combination with the coupler core because of their high coupling rate. In other words, the atomic groups bonded to the coupling positions of general formulas () and () are 2,4
-dioxoimidazolidinyl group, 3,5-dioxotriazolidinyl-4-yl group, 2,4-dioxooxazolidinyl group, imidazolyl group, pyrazolyl group, triazolyl group, benztriazolyl group , phenoxy group, arylthio group, tetrazotetrazolylthio group, alkylthio group, alkoxy group, acyloxy group, and the atomic group bonded to the coupling position of the general formula () and (), (), () is an imidazolyl group. , pyrazolyl group,
triazolyl group, benztriazolyl group, arylthio group, tetrazolylthio group, phenoxy group,
They are alkoxy groups, acyloxy groups, alkylthio groups, and arylazo groups, and have the general formulas (), (
The atomic group bonded to the coupling position of ) and () is an alkoxy group, phenoxy group, arylazo group, arylthio group, tetrazolylthio group, acyloxy group, or alkylthio group, and is bonded to the coupling position of general formulas () and (). Examples of the atomic group include a tetrazolylthio group, a benztriazolyl group, a pyrazolyl group, an arylthio group, an arylazo group, and a phenoxy group. These leaving groups can have the substituents listed as substituents for X in general formulas () and (). Particularly preferred coupler residues are those represented by the general formula (). Next, the compounds of the present invention will be specifically shown, but the invention is not limited thereto. Synthesis example (1) Synthesis of exemplified compound (3) Synthesis of Compound 3~ 1-hydroxy-4-{5-(6-)methoxycarbonylbenzotriazolylmethoxy-2-naphthoic acid (1~) 50g, 2-(3-dodecylthiopropoxy)aniline (2~) 44.7g DMF solution 200ml
and 26.2 g of dicyclohexylcarbodiimide.
20 ml of DMF solution was added dropwise at 0° C. and stirred for 6 hours. Pour the reaction solution into 300ml of water, extract with ethyl acetate,
Washed with aqueous sodium chloride solution. The ethyl acetate layer was dried over magnesium sulfate and then concentrated under reduced pressure.
Crystallization was performed by adding acetonitrile to obtain 49.6 g of the desired product. Synthesis of Compound 4~ To a mixture of Compound 3~, 49.6 g, and 200 ml of ethanol, 200 ml of an aqueous solution of 18.2 g of KOH was added, and the mixture was refluxed for 1 hour. After making the mixture weakly acidic with hydrochloric acid, the precipitated crystals were collected. After washing with acetonitrile, the crystals were dried to obtain 41.0 g of the desired product. Synthesis of Compound 5~ A solution of 11.9 g of dicyclohexylcarbodiimide in 20 ml of methylene chloride was added dropwise to a mixture of 41.0 g of Compound 4~, 54.1 g of phenol, and 1.5 g of methylene chloride at 0°C, and the mixture was stirred for 3 hours and then further stirred for 12 hours at room temperature.
The reaction solution was washed with an aqueous potassium carbonate solution and water to remove excess phenol. Methylene chloride was distilled off under reduced pressure and replaced with ethyl acetate to crystallize the desired product. By washing the obtained crystals with hot methanol, 5 to 34.5 g of the final target product were obtained. (mp124.5-125.5℃) To introduce the coupler of the present invention into the hydrophilic colloid layer, the following high-boiling point support solvent is used as described in the US patent.
2322027, or an organic solvent with a boiling point of about 30°C to 150°C, such as lower alkyl acetate such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β- After being dissolved in ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The following high boiling point organic solvents and low boiling point organic solvents may be used in combination. As the above-mentioned high boiling point solvent, especially an organic solvent having a boiling point of 180° C. or higher, any known one can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate) described in US Pat. No. 2,322,027. , citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), aliphatic esters (e.g. dibutoxyethyl succinate, dioctyl acelate), trimesic acid. Esters (eg tributyl trimesate) and the like are preferred. Particularly preferred are alkyl phosphates (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, etc.). Further, the dispersion method using a polymer described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-open No. 51-59943 can also be used. The coupler of the invention is generally added in an amount of 2 x 10 ^-3 to 5 x 10 -1 mol, preferably 1 x 10 ^-2 to 5 x ^{10 -1 mol} , per mol of silver in the emulsion layer. The undercoat layer of the photographic light-sensitive material of the present invention is a hydrophilic colloid layer made of a hydrophilic polymer such as gelatin (a binder or protective colloid for the photographic emulsion described later is similarly used), and is usually formed on a support. It is applied by applying it to the surface. Generally, by providing an undercoat layer, it is possible to improve adhesion with photographic emulsion layers and prevent halation. The color photographic materials used in the present invention are suitable as long as they are color paper, color negative film, color reversal film, and other color photographic materials that require color development processing, but are particularly suitable for print-sensitized materials (e.g., color paper, etc.). is preferred. The photographic emulsion used in the present invention is written by P. Glafkides.
Chimie et Physique Photographique (Paul
Montel Publishing, 1967), GFDuffin
Photographic Emulsion Chemistry (The Focal
Press, 1966), VLZelikman et al.
Making and Coating Photographic Emulsion
(The Fcoal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the methods for reacting the soluble silver salt and soluble halogen salt include one-sided mixing method, simultaneous mixing method,
Any combination thereof may be used. It is also possible to use a method in which particles are formed in an excess of silver sulfur (so-called back-mixing method).
As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material of the present invention. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. The photographic emulsions used in this invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-membered heteroartic ring nucleus such as a thiobarbituric acid nucleus can be applied. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Typical examples are US Patent No. 2688545, US Patent No. 2977229, US Patent No.
No. 3397060, No. 3522052, No. 3527641, No. 3527641, No. 3522052, No. 3527641, No.
No. 3617293, No. 3628964, No. 3666480, No.
No. 3672898, No. 3679428, No. 3703377, No. 3672898, No. 3679428, No. 3703377, No.
No. 3769301, No. 3814609, No. 3837862, No. 3837862, No. 3814609, No. 3837862, No.
4026707, British Patent No. 1344281, British Patent No. 1507803,
Special Publication No. 43-4936, No. 53-12375, Japanese Patent Publication No. 52-
No. 110618 and No. 52-109925. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (for example, those described in U.S. Pat. No. 2,933,390 and 3,635,721), aromatic organic acid formaldehyde condensates (for example, as described in U.S. Pat. No. 3,743,510) , cadmium salts, azaindene compounds, etc. US patent
No. 3615613, No. 3615641, No. 3617295, No. 3615613, No. 3615641, No. 3617295, No.
The combination described in No. 3635721 is particularly useful. Gelatin is advantageously used as the admixture or protective colloid for photographic emulsions, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal,
Poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. In addition to lime-processed gelatin, acid-processed gelatin, Bull.Soc.Sci.Phot.Japan No.16,
Oxygenated gelatin such as that described on page 30 (1966) may also be used. The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer and at least one blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as necessary. a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer,
It is usual that each blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. In carrying out the present invention, the following known antifading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenols, bisphenols, and the like. The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. The photosensitive material produced using the present invention preferably contains an ultraviolet absorber in the hydrophilic colloid layer.
For example, benzotriazole compounds substituted with aryl groups (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681),
Benzophenone compounds (for example, JP-A-46-2784)
), cinnamate ester compounds (e.g., those described in U.S. Pat.
4,045,229) or benzoxazole compounds (eg, those described in US Pat. No. 3,700,455). Further, those described in US Pat. No. 3,499,762 and Japanese Patent Application Laid-Open No. 54-48535 can also be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These UV absorbers may be mordanted into certain layers. In the photosensitive material produced using the present invention,
The photographic emulsion layer and other hydrophilic colloid layers may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener. These brighteners may be water-soluble, or water-insoluble brighteners may be used in the form of a dispersion. In the photographic material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various known coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used. Any known method can be used for the photographic processing of the light-sensitive material of the present invention. A known treatment liquid can be used. Processing temperature is usually 18
The temperature is selected between 18°C and 50°C, but the temperature may be lower than 18°C or above 50°C. Any color development process that forms a dye image depending on the purpose can be applied. Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino- N-ethyl-N-β
-Hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamide ethylaniline,
4-amino-3-methyl-N-ethyl-N-β-
methoxyethylaniline, etc.) can be used. Other Photography by LFAMason
Processing Chemistry (Focal Press, 1966)
), pp. 226-229, U.S. Patent No. 2193015,
Those described in No. 2592364, JP-A-48-64933, etc. may be used. Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates and phosphates, development inhibitors or antifoggants such as bromides, iodides and organic antifoggants. can. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, It may also contain fogging agents such as sodium borohydride, viscosity-imparting agents, polycarboxylic acid chelating agents as described in US Pat. No. 4,083,723, antioxidants as described in OLS 2,622,950, and the like. After color development, the photographic emulsion layer is usually bleached. Bleaching treatment may be performed simultaneously with fixing treatment, or may be performed separately. As bleaching agents, compounds of polyvalent metals such as iron (), cobalt (), chromium (), copper (), peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron () or cobalt (), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or citric acid, tartaric acid. , complex salts of organic acids such as malic acid; persulfates, permanganates; nitrosophenols, and the like can be used. Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. In addition to a bleach accelerator and a thiol compound, various additives can also be added to the bleach or bleach-fix solution. In order to promote color development, a color developing agent or a derivative thereof may be contained in the sensitive material in advance, for example, in the form of a metal salt or Schiff salt. For example, U.S. Patent No. 3719492, U.S. Pat.
3342559, Research Disclosure 1976 No.
15159, can be used. Further, a developing agent such as hydroquinones, 3-pyrazolidone derivatives, and aminophenol derivatives may be contained in the sensitive material. Example 1 A color photosensitive material having the composition shown below was prepared on a triacetate film support. 1st layer Emulsion layer Silver iodobromide emulsion (silver iodide; 5 mol%)... Silver coating amount 1.5 g/m ² Coupler C-1... 0.1 mol per mol of silver 2nd layer Protective layer Trimethyl methacrylate particles (approx. 1.5 μ in diameter)
Apply a layer of gelatin containing. In addition, gelatin hardening agent H-1 and a surfactant were added to the above layer. The coupler was dissolved by heating in tricresyl phosphate with ethyl acetate as an auxiliary solvent, mixed with a gelatin solution, and then emulsified and dispersed in a colloid mill for use. The sample obtained as above was designated as 101. Preparation of Samples 102 to 108 Samples 102 to 108 were prepared in the same manner as Sample 101 except that the coupler C-1 in the first layer of Sample 101 was replaced with the coupler shown in Table 1 in an equimolar amount. The obtained samples 101 to 108 were wedge exposed with white light and subjected to the processing described below. Gamma and sensitivity of the obtained cyan, magenta, and yellow images (relative logE value of fog + density 0.2)
are shown in Table 1. The couplers used in comparative examples are as follows.

[Table] In all cases, it can be seen that the couplers of the present invention exhibit higher gamma and sensitivity than the comparative couplers, and have higher color development. The development process used here was carried out at 38°C as described below. 1 Color development... 3 minutes 15 seconds 2 Bleaching... 6 minutes 30 seconds 3 Washing with water... 3 minutes 15 seconds 4 Fixing... 6 minutes 30 seconds 5 Washing with water... 3 minutes 15 seconds 6 Stability... The composition of the treatment liquid used in each step is as follows. Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide 1.4g Hydroxylamine sulfate 2.4g 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate Add 4.5g water 1 Bleach solution Ammonium bromide 160.0g Aqueous ammonia (28%) 25.0cc Ethylenediamine-tetraacetic acid sodium iron salt 130.0g Glacial acetic acid 14.0cc Add water 1 Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0cc Sodium bisulfite 4.6g Add water 1 Stabilizer Formalin 8.0cc Add water 1 Example 2 Each layer with the composition shown below was placed on a cellulose triacetate film support. A multilayer color photosensitive material sample was prepared. 1st layer; antihalation layer; gelatin layer containing black colloidal silver; 2nd layer; intermediate layer; gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone; 3rd layer; 1st red-sensitive emulsion layer; odor Silver emulsion (silver iodide; 5 mol%) ...... Silver coating amount 1.6 g/m ² Sensitizing dye... per 1 mol of silver
4.5×10 ^-4 mol Sensitizing dye...for 1 mol of silver
1.5×10 ^-4 mol Coupler EX-1...0.04 mol for 1 mol of silver Coupler EX-3...0.003 mol for 1 mol of silver Coupler C-5...For 1 mol of silver
0.0012 mol 4th layer; 2nd red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 10 mol %)... Silver coating amount 1.4 g/m ² Sensitizing dye... 3x per mol of silver 10 ^-4 mol Sensitizing dye...1 x 10 ^-4 mol per mol of silver Coupler EX-1...0.002 mol per mol of silver Coupler EX-2...0.02 mol per mol of silver Coupler EX- 3...for 1 mole of silver
0.0016 mol 5th layer; Intermediate layer 6th layer same as the 2nd layer; 1st green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 4 mol %)... Silver coating amount 1.2 g/m ² Sensitization Dye... 5 x 10 ^-4 mol per mol of silver Sensitizing dye... 2 x 10 ^-4 mol per mol of silver Coupler EX-4... 0.05 mol per mol of silver Coupler EX-5... 0.008 mol for 1 mol of silver Coupler EX-9...for 1 mol of silver
0.0015 mol 7th layer; 2nd green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 8 mol %)... Silver coating amount 1.3 g/m ² Sensitizing dye... 3x per mol of silver 10 ^-4 mol Sensitizing dye...for 1 mol of silver
1.2×10 ^-4 mol Coupler EX-7...0.017 mol for 1 mol of silver Coupler EX-6...0.003 mol for 1 mol of silver Coupler EX-10...For 1 mol of silver
0.0003 mol 8th layer; Yellow filter layer Colored colloidal silver and 2,5-
Ninth layer of gelatin layer containing an emulsified dispersion of di-t-octylhydroquinone; first blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 6 mol%)... Silver coating amount 0.7 g/m ² Coupler EX-8...0.25 mol for 1 mol of silver Coupler C-6... for 1 mol of silver
0.025 mol 10th layer; 2nd blue-sensitive emulsion layer Silver iodobromide (silver iodide; 6 mol %)... Silver coating amount 0.6 g/m ² Coupler EX-8... 0.06 mol 11th per mol of silver Layer: 1st protective layer Silver iodobromide (silver iodide 1 mol%, average particle size 0.07μ)...Silver coating amount 0.5g/m ² Gelatin layer containing an emulsified dispersion of ultraviolet absorber UV-1 12th layer ;Second protective layer polymethylmethanoacrylate particles (diameter approx.
Apply a gelatin layer containing 1.5μ). In addition to the above composition, each layer contains a gelatin hardening agent H.
-1 and a surfactant were added. The sample prepared as described above was designated as sample 201. Compound used to make the sample Preparation of Samples 202 to 204 Samples 202 to 204 were prepared in the same manner as Sample 201, except that DIR coupler C-5 in the third layer or coupler C-6 in the ninth layer of Sample 201 was replaced with the couplers shown in Table 2 in equimolar amounts. The obtained samples 201 to 204 were subjected to the same treatment as in Example 1 after being wedge exposed to white light. Table 2 shows the gamma of the magenta color image obtained in order to examine the effect of suppressing development on adjacent layers.

[Table] In the case of DIR couplers, the leaving group exhibits development inhibiting properties, so the higher the reactivity, the greater the softening. The results in Table 2 show that the DIR coupler of the present invention has a large softening of tone and high reactivity.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material containing a coupler characterized by having a diffusion-resistant group represented by the following general formula at a bonding position other than the coupling position. -O-(CH ₂ ) _w -S(O) _v -R In the formula, w represents an integer from 2 to 6, v represents an integer from 0 to 2, and R is substituted or unsubstituted with 6 or more carbon atoms. Substituted, linear, cyclic or branched, and saturated or unsaturated alkyl group,
Alternatively, it represents a substituted or unsubstituted aryl group.